Timber preserving agent for maintenance purposes

ABSTRACT

The use of a wood preservative for the afterprotection of wood, comprising a copper compound, a polyamine and an inorganic fungicide, and a bandage for the afterprotection of wood, which contains this wood preservative, is described.

The present invention relates to the use of a wood preservative for theafterprotection of wood, comprising a copper compound, a polyamine andan inorganic fungicide, and a bandage for the afterprotection of wood,which contains this wood preservative.

For the aftercare of transmission-line poles in the supply network ofthe post office and electricity supply companies or similar round woodstocks, in particular in the area of the ground-air zone, bandagescontaining water-soluble wood preservatives are applied. It is known toemploy water-soluble salts based on inorganic fluorine compounds forthis, such as, for example, alkali metal fluorides, in some cases incombination with alkali metal bichromate or boron compounds such asboric acid or borax. These salts, however, are exclusively activeagainst wood-destroying Basidiomycetes, the soft rot activity forinstallation with soil contact is absent. Proposed substances havingsoft rot activity are, on the one hand, dinitrophenol (Barry A.Richardson: Wood preservation--The Construction Press Ltd., Lancaster p.181) or combinations of the abovementioned compounds with water-solublecopper salts such as, for example, copper sulfate or copper acetate.Mixtures of copper sulfate, also in combination with alkali bichromate,with boric acid and copper acetate with alkali metal fluoroborates areprior art. Dinitrophenol has meanwhile been excluded because of itstoxicity.

The water-soluble abovementioned copper compounds on their own, but alsoin the abovementioned combinations, do not have good diffusion poweradequate to penetrate, for example, the sapwood of pine poles, even onlong standing, and to reach the core.

Wood preservatives based on copper and amines as complexing agents havebeen proposed for large-scale impregnation, in particular boilerpressure impregnation.

EP-B 211 181 relates to a wood preservative based on a copper salt andmonoethanolamine for the boiler pressure impregnation of wood.

EP-B 270 848 describes a wood preservative based on a copper compound, acarboxylic acid and an aliphatic polyamine for boiler pressureimpregnation.

EP-A 423 674 describes a wood preservative based on a metal salt of anN-organyldiazeniumdioxy compound and a complex-forming polymeric aminefor the boiler pressure process.

It is common to all the wood preservatives described above that theyhave a high fixing power for the copper in the wood. By means of this,the diffusion power of the copper is restricted, which is why thesesystems are unsuitable for the afterprotection of wood.

Known, currently used systems for the afterprotection of wood contain,for example, combinations of copper naphthenate, boron and fluorinecompounds. An example of this type of product, which is mainly used inthe USA, is CURAP 20 (manufacturer: naK Biotech), a paste which contains18.16% of amine-based copper naphthenate and 40% of sodium tetraboratedecahydrate. Investigations on poles (species of wood Douglas fir orpine) which had been treated with this product showed after a servicelife of from 1 to 3 years that copper for the major part is virtuallyonly distributed near to the surface (0-10 mm) in the wood (withinvestigated penetration depths of up to 25 mm) and these products thusonly have a very restricted diffusion power for copper (Conservingenergy by environmentally acceptable practices in maintaining andprocuring transmission poles. 15th annual report, September 1995, J. J.Morrell, Oregon State University, Corvallis, Oreg.).

The subsequently published WO 96/233636 describes wood preservatives inpaste form, which comprise a fungicidal metal compound and a fungicidalboron compound. The metal compounds also include copper complexed withaminocarboxylic acids or polycarboxylic acids.

The subsequently published WO 96/233635 describes a wood preservativewhich comprises a metal chelate. Copper complexes with amino acids,iminodiacetic acid, ethylenediaminotetraacetic acid, dicarboxylic acidsand polyphosphates are described.

It is an object of the present invention to make available a woodpreservative for the afterprotection of wood, which has a good diffusionpower of the copper in the wood, with good protection at the same timeagainst soft rot and Basidiomycetes.

It is a further object of the present invention to make available abandage which contains this wood preservative for the afterprotection ofwood.

We have found that this object is achieved by a wood preservative basedon a copper compound, a polyamine and an inorganic fungicide, ifappropriate a complex-forming organic carboxylic acid or its ammonium oralkali metal salts, if appropriate further auxiliaries and ifappropriate water for the afterprotection of wood.

These wood preservatives are particularly suitable for theafterprotection and the aftercare of wood and are used as bandages, inthe inoculation injection process, borehole process and paste process.They penetrate the sapwood in the presence of moisture, e.g. soilcontact, and have a good deep action.

Copper compounds which can be used are water-soluble or -insolublecompounds, e.g. copper sulfate, copper acetate, copper citrate, coppernaphthenate, copper hydroxide, copper hydroxycarbonate, copperoxychloride, copper oxide, copper borate, copper fluoride, copperfluoroborate, bis(N-cyclohexyldiazeniumdioxy) copper or mixturesthereof.

Copper hydroxycarbonate, copper hydroxide and mixtures thereof arepreferred.

Copper hydroxide, especially stabilized copper hydroxide (NorddeutscheAffinerie), is particularly preferably used.

The action of the wood preservative can be improved by salts ofN-cyclohexyldiazenium dioxide and other diazenium dioxides, e.g. as thepotassium salt, with copper compounds the abovementionedbis(N-cyclohexyldiazeniumndioxy)copper generally being formed.

The mixtures contain from 0.25 to 20% by weight of copper calculated asthe element. Some of the copper can also be replaced, for example, by acorresponding zinc compound.

Polyamines which can be used are alkyleneamines having 3-9 C atoms and2-4 N atoms such as, for example, ethylenediamine,2-diethylaminoethylamine, diethylenetriamine, triethylenetetramine,tetraethylenepentamine, 1,2-diaminopropane, 1,3-diaminopropane,dipropylenetriamine, tripropylenetetramine,3-(2-aminoethyl)aminopropylamine,N,N'-bis(3-aminopropyl-1,3-propanediamineand alkanolamines such as, for example, aminoethylethanolamine, andmixtures thereof.

Ethylenediamine, diethylenetriamine, 1,3-diaminopropane,dipropylenetriamine, aminoethylethanolamine and mixtures thereof arepreferred.

Suitable inorganic fungicides are boron compounds such as alkali metalborates, aminoborates, boric acid, boric acid esters and B₂ O₃ ;fluorides such as alkali metal fluorides, alkali metal bi-fluorides,silicon fluorides, ammonium fluorides, ammonium hydrogen fluorides;fluoroborates; fluorophosphates; difluorophosphiates and mixturesthereof.

Sodium fluoroborate, potassium fluoroborate, boric acid, sodium fluorideand mixtures thereof are preferred.

Furthermore, complex-forming organic carboxylic acids such ashydroxycarboxylic acids, aminocarboxylic acids, nitrogen-containingpolycarboxylic acids, ammonium or alkali metal salts thereof andmixtures thereof can additionally be used.

Suitable hydroxycarboxylic acids which can additionally be used are, forexample, glycolic acid, lactic acid, tartaric acid, citric acid, malicacid, ammonium or alkali metal salts thereof and mixtures thereof.

Amino acids such as, for example, glycine, sarcosine, ammonium or alkalimetal salts thereof and mixtures thereof can also be additionally used.

Suitable nitrogen-containing complex-forming polycarboxylic acids whichcan additionally be used are, for example, nitrilotriacetic acid (NTA),ethylenediaminetetraacetic acid, (EDTA), diethylenetriaminepentaaceticacid (DPTA), propylenediaminetetraacetic acid (PDTA),hydroxyethylethylenediaminetriacetic acid (HEDTA), β-alaninediaceticacid, ammonium or alkali metal salts thereof and mixtures thereof.

The wood preservatives of the present invention can additionally containfurther auxiliaries such as water, binders, paste-forming agents,organic and inorganic bases, aliphatic carboxylic acids, ammonium oralkali metal salts thereof, plasticizers, fillers, wetting agents,thickeners and mixtures thereof.

The wood preservatives can additionally contain water, which serves toadjust the viscosity and the handling.

Binders and paste-forming agents which can be used are, for example,acrylate resins in the form of aqueous dispersions or powders,plastisols, aminoplastics, phenolic plastics, PVC-containingplasticizers and mixtures thereof.

Organic and inorganic bases which can additionally be used are ammonia,alkali metal hydroxide solution, amines or mixtures thereof. Suitableamines are, for example, mono-, di- and trialkylamines and alsoalkanolamines.

Suitable alkanolamines are, for example, monoethanolamine,diethanolamine, triethanolamine, isopropanolamine.

To improve the flexibility of the wood preservative dried onto a carriermaterial, aliphatic C₅ -C₂₀ -carboxylic acids such as hexanoic acid,heptanoic acid, octanoic acid, nonanoic acid, decanoic acid,2-ethylenepentanoic acid, 2-ethylhexanoic acid, 2-ethylheptanoic acid,isooctanoic acid, isononanoic acid, isodecanoic acid, versatic acids(highly branched monocarboxylic acids), dicarboxylic acids (C₅ -C₂₀)e.g. decanedicarboxylic acid, and sebacic acid, can additionally beused. Polycarboxylic acids such as polyacrylic acids or copolymers ofacrylic acid with, for example, maleic acid and naphthenoic acids arealso suitable.

    ______________________________________                                        Suitable wood preservatives contain, for example                              ______________________________________                                        2-50% by weight, preferably 5-40% by weight, of a copper com-                 pound,                                                                        2-60% by weight, preferably 5-50% by weight, of a polyamine,                  1-65% by weight, preferably 2-55% by weight, of an inorganic                  fungicide,                                                                    0-25% by weight, preferably 1-20% by weight, of an alkali me-                 tal salt of N-cyclohexyldiazenium dioxide,                                    0-35% by weight, preferably 1-30% by weight, of a complex-for-                ming organic carboxylic acid, its ammonium salts or alka-                     li metal salts,                                                               0-45% by weight, preferably 1-20% by weight, of an auxiliary,                 0-50% by weight, preferably 1-40% by weight, of water,                        the sum of all components yielding 100% by weight.                            ______________________________________                                    

If further components are additionally used for the three-partcombination copper compound, polyamine and inorganic fungicide, thefollowing wood preservatives have proven suitable:

    ______________________________________                                        Composition consisting of                                                     ______________________________________                                        a)  5-40% by weight of a copper compound                                          5-35% by weight of a polyamine                                                10-50% by weight of an inorganic fungicide                                    5-25% by weight of a complex-forming organic carboxylic                       acid                                                                          2.5-35% by weight of water;                                                   or                                                                        b)  5-40% by weight of a copper compound                                          5-35% by weight of a polyamine                                                10-50% by weight of an inorganic fungicide                                    5-25% by weight of a complex-forming organic carboxylic                       acid                                                                          2.5-20% by weight of an aliphatic C.sub.5 -C.sub.20 -carboxylic or            dicarboxylic acid                                                             2.5-35% by weight of water;                                                   or especially when using binders and paste-forming agents                 c)  5-40% by weight of a copper compound                                          5-35% by weight of a polyamine                                                5-50% by weight of an inorganic fungicide                                     0-5% by weight of an alkali metal salt of n-cyclohexyl-                       diazeniumdioxide                                                              0-20% by weight of a complex-forming organic carboxylic acid                  5-40% by weight of an auxiliary                                               0-30% by weight of water.                                                 ______________________________________                                    

The wood preservatives, which can be present as concentrates or dilutedwith water as viscous solutions or in the form of pastes, if appropriatealso as a solid salt, is best carried out by pre-dissolving a polyamineand, if appropriate, complex-forming organic carboxylic acids or theirammonium or alkali metal salts and, if appropriate, auxiliaries,especially aliphatic C₅ -C₂₀ -carboxylic or dicarboxylic acids, usingwater. The copper compounds are then dissolved therein. The use of watercan be dispensed with if the substances employed contain sufficientwater (eg. water of crystallization). Solid salts formed from coppercompounds, polyamine and, if appropriate, complex-forming organiccarboxylic acids or their ammonium or alkali metal salts can also beused.

This premixture can even be present as a highly concentrated paste towhich the inorganic fungicides, and if appropriate further auxiliaries,are then added with stirring.

The pH of the wood preservative in the form of the concentrates orpastes is in general between pH 7 and 12. Depending on the application,the concentrates or pastes can on the one hand be applied or introduceddirectly or with addition of binder on to or into a suitable carriermaterial. Suitable carrier materials are, for example, plastic films orwebs, e.g. of glass fiber, polypropylene, polyester or viscose fiber,foam or other porous plastic materials. In this case, the concentratesare applied to the carrier material, for example, by rolling(calendering). Binders which can be used are, for example, acrylateresins in the form of aqueous dispersions, powders; plastisols,aminoplastics, phenolic plastics, PVC-containing plasticizers.

The system concentrate/carrier material is usually then subjected todrying, for example air drying or, for example, in an oven at about100-180° C., the concentrate drying on in highly viscous form and beingbound to the carrier material; this binding can be improved, ifappropriate, by the abovementioned addition of binders, at the same timethe release of wood preservative can be delayed after application bythis means, if necessary, with a high dose of binder.

The concentrates, in particular on addition of binder, can also bepressed in the form of extrudates, dried and cut to length in order toobtain salt cartridges for insertion into wood by means of boreholes,e.g. in the borehole process. It is also possible to produce cartridgesmade of powdered mixtures, e.g. when using spray-dried concentrates orusing powder ed raw materials in the form of pressed articles of salt.

The diffusible pastes and concentrates or cartridges can be used in thevarious methods of afterprotection and aftercare when, in the case ofparticularly endangered wood components, relatively large preservativeintroduction amounts and penetration depths should be achieved incertain areas.

The pastes are suitable for the bandage process, such as single bandagesor multiple bandages, the inoculation injection process, boreholeprocess and the paste process.

Application takes place in the form of preventive or alternativelycontrolling protective treatments in order

a) permanently to protect timber otherwise not treated with woodpreservatives only in specific sections, e.g. roof beam heads;

b) to increase the amounts introduced or penetration depths achieved inthe first treatment in the danger areas;

c) in timber which has already been used in construction to supplementor increase the preservative content from the basic protection after arelatively long standing time (period of use);

d) in timber parts which have been used in construction also to reachthose areas, in particular in the course of a control measure, whichcannot be reached using the customary impregnation process.

The invention is described with the aid of the following examples:

For the tests, the pastes/concentrates were applied in defined amountsto foam as a carrier. The foam with the paste then went through a dryingprocess. The bandage obtained was applied in the soil-air zone afterpreparation to round wood stocks made of pine which had been used inunderground construction. This area was then wound with a self-adhesivePVC film and thus outwardly protected against the penetration of water.

After a standing time of 12 months, the round wood stocks were dug out,repeatedly cut up perpendicular to the grain in the area of the soil-airzone, the wood stock discs were removed and the copper penetration wasdetermined by reacting (spraying) with a 0.2% strength aqueous solutionof 4-(2-azopyridyl)resorcinol monosodium salt (copper reagent).

For the tests, pine round wood stocks having a diameter of at least 20cm and sapwood widths ≧3 cm were used. In each case, an amount of about500 g of concentrate/salt mixture per bandage was applied, the carriermaterial was incorporated with the active compound concentrate such thatit was about 10 cm above the soil level and about 30 cm below the soillevel; the covering film overlapped this area by at least 10 cm in eachcase. The bandage dimensions here were 40 cm×80 cm. Per formulation, atleast 2 bandages were applied to various round wood stocks and testedfor penetration power.

EXAMPLE A

(not according to the invention)

    ______________________________________                                        35% by weight of copper sulfate                                               32% by weight of potassium bichromate                                         30% by weight of boric acid                                                    3% by weight of sodium hydrogen sulfate                                      ______________________________________                                    

The salt was ground, made into a paste with water, acrylate dispersion(50% strength aqueous dispersion of a copolymer of n-butyl acrylate andstyrene) as the binder (10 T concentrate/2 T water/3 T binder), appliedto the foam as carrier and dried at 120° C. for at least 15 min. in acontinuous flow.

The bandages obtained were applied to round wood stocks. The timber wasused for construction after a standing period of 12 months, aftercutting up the average copper penetration was determined.

    ______________________________________                                        Copper penetration after a standing time of 12 months                         ______________________________________                                        round wood                                                                            mean sapwood width:   about 35 mm                                     stock 1a:                                                                             mean copper penetration:                                                                            about 9 mm                                              The core was not reached in any position                              round wood                                                                            mean sapwood width:   about 38 mm                                     stock 2a:                                                                             mean copper penetration:                                                                            about 12 mm                                             The core was not reached in any position                              ______________________________________                                    

EXAMPLE B

(not according to the invention)

    ______________________________________                                        50% by weight of copper suiphate                                              45% by weight of boric acid                                                    5% by weight of sodium hydrogen sulfate                                      ______________________________________                                    

The salt was made into a paste after grinding with water, acrylatedispersion (50% strength aqueous dispersion of a copolymer of n-butylacrylate and styrene) as the binder (10 T concentrate/2 T water/3 Tbinder), applied to the foam and dried at room temperature for at least24 h. The bandages were applied.

    ______________________________________                                        Copper penetration after a standing time of 12 months                         ______________________________________                                        round wood                                                                            mean sapwood width:   about 41 mm                                     stock 1b:                                                                             mean copper penetration:                                                                            about 7 mm                                              The core was not reached in any position                              round wood                                                                            mean sapwood width:   about 37 mm                                     stock 2b:                                                                             mean copper penetration:                                                                            about 9 mm                                              The core was not reached in any position                              ______________________________________                                    

EXAMPLE C

(not according to the invention)

    ______________________________________                                               50% by weight of copper sulfate                                               50% by weight of sodium fluoroborate                                   ______________________________________                                    

The salt was made into a paste after grinding with water, acrylatedispersion (50% strength aqueous dispersion of a copolymer of n-butylacrylate and styrene) as the binder (10 T concentrate(2 T water/3 Tbinder), applied to the foam and dried at room temperature for at least24 h. The bandage was applied.

    ______________________________________                                        Copper penetration after a standing time of 12 months                         ______________________________________                                        round wood                                                                            mean sapwood width:   about 32 mm                                     stock 1c:                                                                             mean copper penetration:                                                                            about 12 mm                                             The core was not reached in any position                              round wood                                                                            mean sapwood width:   about 43 mm                                     stock 2c:                                                                             mean copper penetration:                                                                            about 10 mm                                             The core was not reached in any position                              ______________________________________                                    

EXAMPLE D

(not according to the invention)

    ______________________________________                                        35% by weight of copper acetate                                               65% by weight of potassium fluoroborate                                       ______________________________________                                    

The salt was made into a paste after grinding with water, acrylatedispersion (50% strength aqueous dispersion of a copolymer of n-butylacrylate and styrene) as the binder (10 T concentrate(2 T water/3 Tbinder), applied to the foam and dried at room temperature for at least24 h. The bandage was applied.

    ______________________________________                                        Copper penetration after a standing time of 12 months                         ______________________________________                                        round wood                                                                            mean sapwood width:   about 37 mm                                     stock 1d:                                                                             mean copper penetration:                                                                            about 7 mm                                              The core was not reached in any position                              round wood                                                                            mean sapwood width:   about 42 mm                                     stock 2d:                                                                             mean copper penetration:                                                                            about 11 mm                                             The core was not reached in any position                              ______________________________________                                    

Examples according to the invention

EXAMPLE I

    ______________________________________                                        10% by weight of ethanolamine                                                 10% by weight of ethylenediamine                                              20% by weight of water                                                        10% by weight of copper hydroxycarbonate                                      50% by weight of boric acid                                                   ______________________________________                                    

The concentrate was prepared by stirring and applied to foam and driedat room temperature for at least 24 h. The bandage was applied.

    ______________________________________                                        Copper penetration after a standing time of 12 months                         ______________________________________                                        round wood                                                                             mean sapwood width:   about 33 mm                                    stock I 1:                                                                             mean copper penetration:                                                      virtually identical to the sapwood area                                       The core is reached                                                  round wood                                                                             mean sapwood width:   about 35 mm                                    stock I 2:                                                                             mean copper penetration:                                                      virtually identical to the sapwood area                                       The core is reached                                                  ______________________________________                                    

EXAMPLE II

    ______________________________________                                        25.00% by weight of aminoethylethanolamine                                    16.65% by weight of water                                                      8.35% by weight of copper hydroxycarbonate                                   50.00% by weight of boric acid                                                ______________________________________                                    

The concentrate was prepared by stirring, applied to foam and dried atroom temperature for at least 24 h. The bandage was applied.

    ______________________________________                                        Copper penetration after a standing time of 12 months                         ______________________________________                                        round wood                                                                             mean sapwood width:   about 41 mm                                    stock II 1:                                                                            mean copper penetration:                                                      virtually identical to the sapwood area                                       The core is reached                                                  round wood                                                                             mean sapwood width:   about 31 mm                                    stock II 2:                                                                            mean copper penetration:                                                      virtually identical to the sapwood area                                       The core is reached                                                  ______________________________________                                    

EXAMPLE III

    ______________________________________                                        32.50% by weight of aminoethylethanolamine                                    10.00% by weight of lactic acid                                               17.00% by weight of water                                                     25.00% by weight of boric acid                                                15.50% by weight of Cu(OH).sub.2, commercially available,                     stabilized (Manufacturer: Norddeutsche                                        Affinerie)                                                                    ______________________________________                                    

The concentrate was prepared by stirring and applied to foam and driedat room temperature for at least 24 h. The bandage was applied.

    ______________________________________                                        Copper penetration after a standing time of 12 months                         ______________________________________                                        round wood                                                                            mean sapwood width:   about 38 mm                                     stock III 1:                                                                          mean copper penetration: virtually the                                        entire sapwood area was covered and the                                       core boundary was reached.                                            round wood                                                                            mean sapwood width:   about 33 mm                                     stock III 2:                                                                          mean copper penetration: virtually the                                        entire sapwood area was covered and the                                       core boundary was reached                                             ______________________________________                                    

EXAMPLE IV

    ______________________________________                                        7.70% by weight of dipropylenetriamine                                        9.80% by weight of water                                                      2.50% by weight of isooctanic acid                                            2.50% by weight of malic acid                                                 1.00% by weight of N-cyclohexyldiazeniumdioxy-                                potassium                                                                     5.50% by weight of copper hydroxide, commercially                             available, stabilized (Manufacturer:                                          Norddeutsche Affinerie)                                                       38.00% by weight of sodium fluoride                                           33.00% by weight of polyvinyl chloride powder                                 (Vinnolit P 4472 from Vinnolit)/                                              bis-(2-ethylhexyl)phthalate premixture                                        (mixing ratio: about 4:5)                                                     ______________________________________                                    

A paste was prepared by stirring, applied to foam and dried at 130° C.for at least 15 min. in a continuous flow oven. The bandage was applied.

    ______________________________________                                        Copper penetration after a standing time of 12 months                         ______________________________________                                        round wood                                                                            mean sapwood width:   about 40 mm                                     stock IV 1:                                                                           mean copper penetration: virtually the                                        entire sapwood area was covered and the                                       core boundary was reached.                                            round wood                                                                            mean sapwood width:   about 35 mm                                     stock IV 2:                                                                           mean copper penetration: virtually the                                        entire sapwood area was covered and the                                       core boundary was reached                                             ______________________________________                                    

The following examples afford a correspondingly good diffusion power.

EXAMPLE V

    ______________________________________                                        14.2%     by weight of dipropylenetriamine                                    8.9%      by weight of malic acid                                             18.9%     by weight of copper hydroxide carbonate                                       [Cu(OH).sub.2 CuCO.sub.3 ]                                          100%      by weight of water                                                  35.0%     by weight of sodium fluoride                                        13.0%     by weight of boric acid                                             ______________________________________                                    

Deviating from the previously mentioned applications, this time 500 g ofthe similarly prepared paste were applied directly to the round woodstock and covered with a plastic film. The incorporation conditions wereidentical to those described previously.

    ______________________________________                                        Copper penetration after a standing time of 12 months                         ______________________________________                                        Round wood                                                                              mean sapwood width: about 39 mm                                     stock V 1:                                                                              mean copper penetration: virtually the entire                                 sapwood area was covered and the core boundary                                was reached.                                                        Round wood                                                                              mean sapwood width: about 37 mm                                     stock V 2:                                                                              mean copper penetration: virtually the entire                                 sapwood area was covered and the core boundary                                was reached.                                                        ______________________________________                                    

EXAMPLE VI

    ______________________________________                                        22.50%   by weight of 1,3-diaminopropane                                      24.00%   by weight of water                                                   10.00%   by weight of malic acid                                              3.50%    by weight of N-cyclohexyldiazeniumdioxy-                                      potassium                                                            15.00%   by weight of copper hydroxide, commercially                                   available, stabilized (Manufacturer:                                          Norddeusche Affinerie)                                               25.00%   by weight of boric acid                                              ______________________________________                                    

A paste was prepared by stirring, applied to foam and dried in acontinuous flow oven at 140° C.

EXAMPLE VII

    ______________________________________                                        22.50%   by weight of 1,3-diaminopropane                                      21.00%   by weight of water                                                   7.50%    by weight of nitrilotriacetic acid                                   4.00%    by weight of N-cyclohexyldiazenium-                                           dioxy-potassium                                                      5.00%    by weight of glycerol                                                25.00%   by weight of boric acid                                              15.00%   by weight of copper hydroxide,                                                commercially available, stabilized                                            (Manufacturer: Norddeutsche Affinerie)                               ______________________________________                                    

A paste was prepared by stirring, applied to foam and dried for at least15 min in a continuous flow oven at 130° C.

EXAMPLE VIII

    ______________________________________                                        17.00%   by weight of 1,3-diaminopropane                                      7.00%    by weight of monoethanolamine                                        26.00%   by weight of water                                                   8.50%    by weight of malic acid                                              2.50%    by weight of bis(N-cyclohexyldiazenium-                                       dioxy)copper                                                         25.00%   by weight of boric acid                                              14.00%   by weight of copper hydroxide, commercially                                   available, stabilized (Manufacturer:                                          Norddeutsche Affinerie)                                              ______________________________________                                    

A paste was prepared by stirring, applied to foam and dried for at least10 minutes in a continuous flow oven at 130° C.

EXAMPLE IX

    ______________________________________                                        16.70%   by weight of dipropylenetriamine                                     11.80%   by weight of water                                                   8.00%    by weight of isooctanoic acid                                        5.00%    by weight of malic acid                                              16.60%   by weight of boric acid                                              8.60%    by weight of copper hydroxide, commercially                                   available, stabilized Manufacturer:                                           Norddeutsche Affinerie)                                              33.30%   by weight of polyvinyl chloride powder                                        (Vinnolit P 4472 from Vinnolit)/bis(2-                                        ethylhexyl) phthalate premixture                                              (mixing ratio: about 4:5)                                            ______________________________________                                    

A paste was prepared by stirring, applied to foam and dried for at least15 min at 130° C. in a continuous flow oven.

EXAMPLE X

    ______________________________________                                        18.5%    by weight of dipropylenetriamine                                     5.3%     by weight of water                                                   7.7%     by weight of isooctanoic acid                                        7.5%     by weight of malic acid                                              11.5%    by weight of copper hydroxide, stabilized                            36.5%    by weight of sodium fluoride                                         13.0%    by weight of boric acid                                              ______________________________________                                    

A paste was prepared by stirring, applied to foam and dried for at least15 min in a continuous flow oven at 130° C.

EXAMPLE XI

    ______________________________________                                        15.4%    by weight of dipropylenetriamine                                     23.9%    by weight of water                                                   35.7%    by weight of copper citrate (about 35% Cu)                                    (copper (II) citrate 2,5-hydrate)                                    25.0%    by weight of boric acid                                              ______________________________________                                    

A paste was prepared by stirring, applied to foam and dried for at least15 min in a continuous flow oven at 130° C.

EXAMPLE XII

    ______________________________________                                        16.5%    by weight of diethylenetriamine                                      27.5%    by weight of water                                                   15.0%    by weight of malic acid                                              16.0%    by weight of copper hydroxide, stabilized                            25.0%    by weight of boric acid                                              ______________________________________                                    

A paste was prepared by stirring, applied to foam and dried for at least15 min in a continuous flow oven at 130° C.

EXAMPLE XIII

    ______________________________________                                        21.0%    by weight of dipropylenetriamine                                     28.0%    by weight of water                                                   13.2%    by weight of citric acid monohydrate                                 16.8%    by weight of copper hydroxide (stabilized)                           21.0%    by weight of Polybor (Na.sub.2 B.sub.9 O.sub.13 x 4 H.sub.2          ______________________________________                                                 O)                                                               

A paste was prepared by stirring, applied to foam and dried for at least15 min in a continuous flow oven at 130° C.

EXAMPLE XIV

    ______________________________________                                        19.0%    by weight of dipropylenetriamine                                     11.9%    by weight of malic acid                                              16.9%    by weight of copper hydroxide carbonate                              32.2%    by weight of water                                                   20.0%    by weight of sodium fluoride                                         ______________________________________                                    

A paste was prepared by stirring, applied to foam and dried for at least15 min in a continuous flow oven at 130° C.

We claim:
 1. A process for the afterprotection of wood, which comprisestreating the wood with an effective wood preserving amount of a woodpreservative composition comprising a copper compound, a polyamine oralkanolamine having at least two nitrogen atoms, and an inorganicfungicide, the treatment being effected by means of a bandaging process,an inoculation injection process, a borehole process or a paste process.2. The process defined in claim 1, wherein the wood preservativecomposition further comprises a complex forming organic carboxylic acid.3. The process defined in claim 1, wherein the copper compound isselected from the group consisting of copper sulfate, copper acetate,copper citrate, copper naphthenate, copper hydroxide, copperhydroxycarbonate, copper oxychloride, copper oxide, copper borate,copper fluoride, copper fluoroborate, bis(N-cyclohexyldiazeniumdioxy)copper and mixtures thereof.
 4. The process defined in claim 1, whereinthe polyamine or alkanolamine is selected from the group consisting ofC₂ -C₉ alkylenepolyamine, alkanolamine and mixtures thereof.
 5. Theprocess defined in claim 1, wherein the polyamine or alkanolamine isselected from the group consisting of ethylenediamine,2-diethylaminoethylamine, diethylenetriamine, triethylenetetramine,tetraethylpentamine, 1,2-diaminopropane, 1,3-diaminopropane,dipropylenetriamine, tripropylenetetramine,3-(2-aminoethyl)aminopropylamine,N,N'-bis(3-aminopropyl)-1,3-propanediamine, aminoethylethanolamine andmixtures thereof.
 6. The process defined in claim 5, wherein thepolyamine or alkanolamine is selected from the group consisting ofethylenediamine, diethylenetriamine, 1,3-diaminopropane,dipropylenetriamine, aminoethylethanolamine and mixtures thereof.
 7. Theprocess defined in claim 1, wherein the inorganic fungicide is selectedfrom the group consisting of boron compounds, fluorides, fluoroborates,fluorophosphates, difluorophosphates and mixtures thereof.
 8. Theprocess defined in claim 2, wherein the complex-forming organiccarboxylic acid is selected from the group consisting ofhydroxycarboxylic acids, aminocarboxylic acids, nitrogen-containingpolycarboxylic acids, ammonium and alkali metal salts thereof andmixtures thereof.
 9. The process defined in claim 8, wherein thecomplex-forming organic carboxylic acid is selected from the groupconsisting of glyoxylic acid, lactic acid, malic acid, tartaric acid,citric acid, nitriloacetic acid, ethylenediaminetetraacetic acid,diethylenetriaminepentaacetic acid, propylenediaminetetraacetic acid,hydroxyethylethylenediaminetriacetic acid, β-alaninediacetic acid,sarcosine, glycine ammonium and alkali metal salts thereof and mixturesthereof.
 10. The process defined in claim 1, wherein the woodpreservative composition further comprises auxiliaries selected from thegroup consisting of water, binders, paste-forming agents, organic andinorganic bases, aliphatic carboxylic acids, plasticizers, fillers,wetting agents, thickeners and mixtures thereof.
 11. The process definedin claim 1, wherein the wood preservative composition consists offrom 2to 50% by weight of one or more copper compounds, from 2 to 60% byweight of one or more polyamines or alkanolamines, from 1 to 65% byweight of one or more inorganic fungicides, from 0 to 25% by weight ofone or more alkali metal salts of N-cyclohexyldiazenium dioxide, from 0to 35% by weight of one or more complex-forming organic carboxylic acidsor ammonium or alkali metal salts thereof, from 0 to 25% by weight ofone or more auxiliaries, and from 0 to 50% by weight of water.
 12. Theprocess defined claim 1 wherein the treatment is effected by means ofthe bandaging process.
 13. A bandage for the afterprotection of wood,comprising an effective wood preserving amount of a wood preservativecomposition comprising a copper compound, a polyamine or alkanolaminehaving at least two nitrogen atoms, and an inorganic fungicide.
 14. Thebandage defined in claim 13, wherein the wood preservative compositionfurther comprises a complex forming organic carboxylic acid.
 15. Thebandage defined in claim 13, wherein the copper compound is selectedfrom the group consisting of copper sulfate, copper acetate, coppercitrate, copper naphthenate, copper hydroxide, copper hydroxycarbonate,copper oxychloride, copper oxide, copper borate, copper fluoride, copperfluoroborate, bis(N-cyclohexyldiazeniumdioxy) copper and mixturesthereof.
 16. The bandage defined in claim 13, wherein the polyamine oralkanolamine is selected from the group consisting of C₂ -C₉alkylenepolyamine, alkanolamine and mixtures thereof.
 17. The bandagedefined in claim 13, wherein the polyamine or alkanolamine is selectedfrom the group consisting of ethylenediamine, 2-diethylaminoethylamine,diethylenetriamine, triethylenetetramine, tetraethylpentamine,1,2-diaminopropane, 1,3-diaminopropane, dipropylenetriamine,tripropylenetetramine, 3-(2-aminoethyl)aminopropylamine,N,N'-bis(3-aminopropyl)-1,3-propanediamine, aminoethylethanolamine andmixtures thereof.
 18. The bandage defined in claim 17, wherein thepolyamine or alkanolamine is selected from the group consisting ofethylenediamine, diethylenetriamine, 1,3-diaminopropane,dipropylenetriamine, aminoethylethanolamine and mixtures thereof. 19.The bandage defined in claim 13, wherein the inorganic fungicide isselected from the group consisting of boron compounds, fluorides,fluoroborates, fluorophosphates, difluorophosphates and mixturesthereof.
 20. The bandage defined in claim 14, wherein thecomplex-forming organic carboxylic acid is selected from the groupconsisting of hydroxycarboxylic acids, aminocarboxylic acids,nitrogen-containing polycarboxylic acids, ammonium and alkali metalsalts thereof and mixtures thereof.
 21. The bandage defined in claim 20,wherein the complex-forming organic carboxylic acid is selected from thegroup consisting of glyoxylic acid, lactic acid, malic acid, tartaricacid, citric acid, nitriloacetic acid, ethylenediaminetetraacetic acid,diethylenetriaminepentaacetic acid, propylenediaminetetraacetic acid,hydroxyethylethylenediaminetriacetic acid, β-alaninediacetic acid,sarcosine, glycine ammonium and alkali metal salts thereof and mixturesthereof.
 22. The bandage defined in claim 13, wherein the woodpreservative composition further comprises auxiliaries selected from thegroup consisting of water, binders, paste-forming agents, organic andinorganic bases, aliphatic carboxylic acids, plasticizers, fillers,wetting agents, thickeners and mixtures thereof.
 23. The bandage definedin claim 13, wherein the wood preservative composition consists offrom 2to 50% by weight of one or more copper compounds, from 2 to 60% byweight of one or more polyamines or alkanolamines, from 1 to 65% byweight of one or more inorganic fungicide, from 0 to 25% by weight ofone or more alkali metal salt of N-cyclohexyldiazenium dioxide, from 0to 35% by weight of one or more complex-forming organic carboxylic acidsor ammonium or alkali metal salts thereof, from 0 to 25% by weight ofone or more auxiliaries, and from 0 to 50% by weight of water.